Hydroxyphenylaminoanthracenes



Patented Sept. 29, 1936 PATET OFFICE HYDROXYPHENYLAIVIINOANTHRACENESWalter Hagge and Karl Haagen, Des sau in Anhalt, Germany, assignors toGeneral Aniline Works, Inc., New York, a corporation of Delaware NoDrawing. Application June 15, 1935, Serial No. 26,801. In Germany June23, 1934 8 Claims.

Our present invention relates to a process for manufacturinghydroxyarylaminoanthracenes and to the new products obtainable by thisprocess.

More particularly it relates to a process which comprises condensing ahydr-oxy or aminoanthracene in the presence of a bisulfite solution witha hydroxyaminobenzene.

The condensation reaction discovered by Bucherer and his co-workers, onwhich this process is based, namely the reaction of an aromatic amino orhydroxy compound with a sulfite, was not, according to the authors(Journal fiir praktische Chemie, vol. '71, page 443) extended to theanthraquinone series.

Now, We have found that a hydroxy or aminoanthracene may be condensedwith a hydroxyaminobenzene by boiling these starting materials togetherwith a bisulfite solution under reflux or in a closed vessel underpressure. In this manner there are obtained hitherto unknown compoundswhich are useful as intermediate products in the manufacture of dyes.

The following examples illustrate the invention, the parts being byweight unless otherwise stated and the parts by weight and parts byvolume having the relationship which exists between the kilo and theliter:-

Example 1.285 parts of 2-hydroxyanthracene-3-carboxylic acid, 2000 partsby volume of bisulfite lye of B. and 170 parts of4-amino-lhydroxybenzene are heated together under reflux in an openvessel for 38 hours while stirring. The whole is allowed to cool toabout 70 C., the condensation product is filtered and washed withhotwater. The yield of 4-hydroxyphenyl-2-aminoanthracene is 334 partsand corresponds with 98 per cent. of the theoretical yield.

Example 2.-120 parts of l-hydroxyanthracene, 85 parts of4-amino-l-hydroxybenzene and 875 parts by volume of a sodium bisulfitelye of 25 B. mixed with 12 parts of sodium carbonate are together heatedin a lead-lined stirring vessel for 40 hours under pressure at 120 C.After cooling the contents of the vessel to about 70 C., they arefiltered and the solid matter is washed with hot water. There areobtained 95 parts of 4-hydroxyphenyl-l-aminoanthracene, whichcorresponds with 54 per cent. of the theoretical yield.

Example 3.-1 19 parts of 2-hydroxyanthracene-3-carboxylic acid, asolution of 149 parts of 2-chloro-4-amino -1- hydroxybenzene -6-sulfonic acid in 1000 parts by volume of bisulfite lye of 25 B. and 50parts by volume of sodium hydroxide solution of 35 B., are heatedtogether as described in Example 1, stirring, for 42 hours.

After cooling to about C., the mass is filtered and from the solidmatter the excess of chloroaminophenol-sulfonic acid is washed with hotwater. The yield of 3'-ch.loro4-hydroxyphenol2-aminoanthracene-5'-sulfonic acid amounts to about per cent. of thetheoretical yield.

It is obvious that our invention is not limited to the foregoingexamples or to the specific details given therein. Thus, for instance,the concentration of the bisulfite lye, the temperature at which thereaction mixture is kept, and correspondingly the time of reaction maybe varied within certain limits. Furthermore, it is not necessary that achemically pure bisulfite lye may be used, the technical alkalibisulfite products, which contain a certain amount of neutral sulfitecan be used in the same manner. Finally, the aminohydroxybenzene whichis to be condensed with hydroxyor aminoanthracenes may be the orthoormeta-compound and it may contain other substituents, such as alkyl. Inthe foregoing examples the aminoanthracenes may be used instead of thehydroxy compounds.

What we claim is:--

1. The compounds which correspond to the general formula under refluxand while in which R is a member of the group consisting of phenyleneradical and homologues thereof. 2. The compounds which correspond to thegeneral formula 3. 4-I-Iydroxyphenyl-l-aminoanthracene.

4. 4-Hydroxyphenyl-Z-aminoanthracene.

5. The process which comprises heating an anthracene compound of thegeneral formula in which X is a member of the group consisting of OH andNH2, and Y is a member of the group consisting of H and COOH, with ahydroxyaminobenzene in the presence of an alkali metal bisulfitesolution.

6. The process which comprises heating an anthracene compound of thegeneral formula in which X is a member of the group consisting of OH andNH2, and Y is a member of the group WALTER HAGGE. KARL HAAGEN.

DISCLAIMER 2,055,792.Walter Hagge and Karl Haagen, Dessau in Anhalt,Germany. HYDROXY- PHENYLAMINOANTHRACENES. Patent dated September 29,1936. Disclaimer filed July 22, 1937, by the assignee, General Aniline lVorlcs, Inc.

Hereby enters this disclaimer to certain of the claims of the aboveidentified patent, and

Hereby disclaims claim 4.

Hereby disclaims from the scope of claims 1 and 2 all compoundscorresponding to the stated formula wherein the amino nitrogen atom isattached to a beta-carbon atom of the anthracene nucleus.

Hereby disclaims from the scope of claims 5 and 6 all processesemploying anthracene compounds corresponding to the stated formulawherein X is attached to a beta-carbon atom of the anthracene nucleus.

(Ofiicial Gazette August 24, 1.937.)

